CN106310364A - Degradable magnesium/strontium-containing sulfate-apatite porous composite biological scaffold - Google Patents

Degradable magnesium/strontium-containing sulfate-apatite porous composite biological scaffold Download PDF

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CN106310364A
CN106310364A CN201610525104.3A CN201610525104A CN106310364A CN 106310364 A CN106310364 A CN 106310364A CN 201610525104 A CN201610525104 A CN 201610525104A CN 106310364 A CN106310364 A CN 106310364A
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magnesium
strontium
source
sulfur
calcium
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CN106310364B (en
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李桑
蒋国强
汤亭亭
傅俊
彭兆祥
毛海蛟
熊汉锋
聂磊
李亚屏
郑建民
张国锋
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Abstract

The invention discloses a degradable magnesium/strontium-containing sulfate-apatite porous composite biological scaffold which is prepared by the following steps: treating a bovine calcined cancellous bone mineral porous scaffold by a magnesium-source/strontium-source/sulfur-source-containing quaternary system, taking out, drying, and carrying out high-temperature calcination. The degradable magnesium/strontium-containing sulfate-apatite porous composite biological scaffold has a favorable three-dimensional intercommunication mesh structure, and has favorable osteoconductivity, degradability, mechanical strength and biocompatibility. The high-length-diameter-ratio calcium sulfate whiskers growing in the meshes can increase the specific area of the material, thereby possibly improving the cell adhesion. The composite biological scaffold has favorable bone repair effects in the animal bone defect region, and does not have inflammatory reaction or immunological rejection reaction. The composite biological scaffold can satisfy the ideal conditions for bone transplantation alternate materials or bone tissue engineering scaffold materials.

Description

A kind of degradable contains magnesium and the sulfur apatite porous compound bio support of strontium
Technical field
The present invention relates to field of medical materials, compound raw particularly to a kind of degradable sulfur apatite porous containing magnesium and strontium Thing support.
Background technology
Bone collection is only less than the tissue transplantation of blood transfusion, and the research of bone alternate material, exploitation are the weights of current medical research One of point, is just related to the research of bone alternate material and the body mechanism of action in country of China 12 brainstorm project.
There are the elements such as Ca, P, O, H, C, S, Fe, Mg, Cu, Si, Zn, Mn, Na, K in structure adult bone bone ore deposit, in people's bone mineralising mistake There is homogeneity replacement widely in journey, people's bone has composition and the structure of complexity.At bone tissue engineering scaffold or artificial bone Design process in, it is critical to consider the complicated composition of this serious mineralized tissue of people's bone and structure；People's bone can not be by single material The finite nature that material is provided substitutes completely, it is even more important that support must also provide three-dimensional many for the regeneration of osseous tissue Hole micro structure is to guide the differentiation and proliferation of cell, and wants to maintain or comparatively fast the enough mechanical strengths of acquirement meet and substituted The mechanical requirements of material.Preferably bone transplantation substitute material or bone tissue engineering stent material should have a following condition: 1) have Good bone conductibility, it is mesh-structured that material has aperture preferably three-dimensional intercommunication, the highest porosity and specific surface area 2) there is osteoinductive；3) there is good biocompatibility and support bone cell growth and the surface chemistries of function differentiation Matter and micro structure；4) there is good biological degradability；5) part undertaking bone conduction effect in material must have enough power Learn intensity and bearing capacity；6) easy processing etc..
Johan etc. are summarized as four clinical for New Zealand available bone transplantation substitute material in 2010 in a summary Class: 1, single-phase calcium phosphate material includes that three kinds of hydroxyapatite inverting biological pottery, synthesizing hydroxylapatite cement are a kind of, β-phosphoric acid DFP Artificial Ceramic two kinds；2, composite includes that tetracalcium phosphate/calcium hydrogen phosphate, 62.5% type alpha tricalcium phosphate/26.8% are anhydrous Calcium hydrogen phosphate/8.9% calcium carbonate/1.8% hydroxyapatite, 60% hydroxyapatite/40%b-tricalcium phosphate, 73%b-phosphoric acid DFP/21% dalcium biphosphate/5% magnesium hydrogen phosphate, tetracalcium phosphate/calcium hydrogen phosphate/amorphous calcium phosphate, type alpha tricalcium phosphate/carbon The synthesis cement 6 kinds of the formula such as acid calcium/dalcium biphosphate, formula is the Artificial Ceramic of 80% tricalcium phosphate/20% calcium hydrogen phosphate A kind of；3, the mud cream that prepared by single-phase calcium sulfate or granule totally four kinds；4, siliceous bio-vitric is a kind of.Apatite, calcium sulfate are mesh Before the most most commonly seen bone transplantation substitute material or constituent.Clinic lacks preferable bone transplantation substitute material at present, Be mainly manifested in ideal three-dimensional intercommunication porosity mesh-structured, great and specific surface area, degradability, bone conductibility, bone lure The characteristic such as the property led and mechanical strength is many can not have both at the same time.
The clinical artificial bone with ideal three-dimensional intercommunication mesh micro structure applied is animal material and converts : two of which derives from the Porous Hydroxyapatite Ceramic bone that bovine cancellous bone is prepared through high temperature sintering operation, and feature is Remain the three-dimensional intercommunication mesh micro structure in bovine cancellous bone natural bone ore deposit and composition close to people's bone bone ore deposit composition, there is good life The thing compatibility, good bone conductibility and preferable incompressible intensity, exempt from but bone-xenograft immunologic rejection because of high temperature sintering program anti- Answer and pathogen imports possible, and be prone to processing.Porous hydroxyapatite from Os Bovis seu Bubali has the good hole of 60-90% Rate and Os Bovis seu Bubali aboundresources, its aperture is 390-1360 μm, slightly larger than bone transplantation substitute material and the osseous tissue work of 150-400 μm The preferable aperture of engineering support；Possesses the good incompressible intensity of 1-20MPa；Beneficially Bone Defect Repari cell implanted in the body is raised Collection, the entrance of blood vessel, oxygen and the exchange of tissue fluid, provide good physiological activity space to prop up with sticking for Bone Defect Repari cell Hold；Its huge shortcoming is that the bone ore deposit hydroxyapatite that high temperature sintering bovine cancellous bone obtains is the most stable, and degradation in vivo is too Crossing slow long, in calcium phosphorus kind bone-grafting material, dissolubility is minimum, and degradation speed can not also can not with new bone formation speeds match far away The useful ions of skeletonization such as sustained release higher concentration calcium, therefore lack good osteogenic activity, be unfavorable for reparation and the transformation of bone.
Preferably degradation speed is another important requirement of artificial bone or bone tissue engineering scaffold, and preferable artificial bone is degraded Speed should match with new bone formation speed, is gradually degraded to new bone replacement and further provides for while guiding new bone formation Space, in its degradation process, redeposited, the transformation that the useful ion of skeletonization is bone ore deposit such as the calcium ion of constantly release carry with metabolism For mineral restructuring composition, this process may stimulate new bone formation i.e. possess the most potential osteoinductive；Artificial bone or Too fast support and the guiding being unfavorable for Bone Defect Repari process provides enough space-time of engineering material of bone tissue degradation speed, and degraded Slow then the formation of new bone, replacement and moulding can be hindered.The degraded in vivo of inorganic matter bone-grafting material is mainly by two approach: body The molten fall of liquid mediation and cell-mediated degradation process.Molten fall process is under the effect of body fluid, material and binding agent hydrolysis, material Material is progressively dissociated into the physics molten fall process of granule, molecule, ion.And cell-mediated degradation process be mainly macrophage and The osteoclast phagocytotic biodegradation process to material.Inorganic matter bone-grafting material degradation process in vitro forms with it Composition is relevant, and its degradation speed also has close phase with the granular size of material, porosity, specific surface area, degree of crystallinity and dissolubility Closing, wherein dissolubility is most important influence factor.In the most most commonly seen bone transplantation substitute material, calcium sulfate has The fastest degradation speed [the calcium sulfate the most degradable time is 45-72d, and twice faster than autologous bone is many], in calcium phosphate material Hydroxyapatite there is the slowest degradation speed [atresia bulk hydroxyapatite in vivo 10 years all can not be degradable], have Much larger than new bone formation speed, other calcium phosphorus compositions such as tricalcium phosphate, calcium hydrogen phosphate, dalcium biphosphate, polyphosphoric acids hydrogen calcium, Jiao The degradation rate of calcium phosphate etc. is between the two, possesses the degradation speed of rather moderate.In order to overcome calcining bovine cancellous bone porous The distinct disadvantage of hydroxyapatite, over nearly 20 years, has scientist to attempt calcining bovine cancellous bone porous hydroxyapatite and turns Turn to the complex phase Apatite Ceramic of tricalcium phosphate or phosphoric acid DFP.It is commonly called as the simple substance calcium sulfate mud cream of Paris cement, cement Grain is to be applied to the material the most remote that Cranial defect is filled, because of 1, good resistance to biology；2 good space filling characteristics；3 relatively Fast infiltration rate and bio-absorbable are complete；4, potential osteogenic activity；5 good bone conduction effect and because absorb faster Space can be provided to adopt so far for Bone Defect Repari.Calcium sulfate is dissolved solution about 0.2 gram, calcium sulfate body in 100 milliliters of water Being partially formed high calcium environment during interior degraded, being formed for freshman bone tissue's bone ore deposit provides calcium source, ties with the phosphate radical in body fluid etc. Close thus promote the mineralising of new bone, its potential bone-inducting active and local high calcium, meta-acid microenvironment in calcium sulfate course of dissolution Relevant；Calcium sulfate degradation in vivo is while the high calcium environment being partially formed provides calcium source for new bone formation, the most in various degree Promote osteoblast to be formed, break up；Calcium sulfate degradation in vivo forms local meta-acid microenvironment may promote people's bone bone ore deposit slightly soluble Fall, causes osteogenic activity albumen to appear, and beneficially new bone formation；But calcium sulfate mud cream or the granule of clinical application at present are same It is mesh-structured that the common drawback having synthetic material is i.e. difficult to possess ideal three-dimensional intercommunication, simultaneously the degradable time in calcium sulfate body For 45-72d, twice faster than autologous bone is many, it is difficult to lasting, stable bone conduction support is done in the formation to new bone, it is impossible to for bone group The regeneration knitted provides three-dimensional porous micro structure i.e. to lack the architecture basics repair cell of good bone conductibility, blood vessel enters and transplants In thing, it is unfavorable for the biological formation of vertical new bone；Even if being successfully prepared as the three-dimensional intercommunication mesh knot of high porosity, high-specific surface area The calcium sulfate simple substance support of structure, its degradation speed can faster, and intensity is worse；Local microenvironment also can be made after the molten fall of calcium sulfate material Meta-acid and likely cause inflammatory reaction.The advantage of synthetic composite material be can by select different degradation characteristic composition and Composition composition, makes the physical property such as the degradation rate of composite, pH value reach certain balance, and may adsorb more kinds of people Activity in vivo albumen (signal protein), improves the biological activity of material, meets the desirable of bone transplantation substitute material more.
It addition, the biological activity of calcium phosphate and other biological sill may be enhanced because mixing bioactive ions.? Some research shows, these bioactive ions energy effective stimulatory protein(SP) activity, promotes cell growth and osteogenesis.Low dosage Strontium there is promoting bone growing, the dual function of suppression bone resorption.Low dosage is replaced part calcium in apatite and is obtained and contain Hydroxyapatite, not only has than the more preferable histocompatibility of pure ha, bone conductibility, even has to a certain degree On osteoinductive.Human body about contains 25g magnesium, and magnesium is formed at human bone and all growth courses, safeguards osteocyte structure and merit Can, bone metabolism and reinvent aspect there is important function.The magnesium phosphate calcio bone cement of low magnesium content can significantly improve cell Adhesive capacity.Mix magnesium calcium phosphate bone cement because can promoting that embedded material and osseous tissue boundary face become and being increasingly subject to pay attention to New type bone reparing biological material: mix magnesium bone cement and be easier to preparation, the existing 73%b-tricalcium phosphate of the western countries such as New Zealand/ The bone cement of 21% dalcium biphosphate/5% magnesium hydrogen phosphate formula is applied clinically.The compound prescription bone cement containing magnesium possesses fall Xie Xing, the bone formation beneficial element such as releasable calcium, phosphorus, magnesium, can carry out after transplanting degrading in body, ion exchange, not have Standby three-dimensional intercommunication is mesh-structured and hinders repair cell and blood vessel to go deep into intra-graft in early days, lacks good bone conductibility The three-dimensional mesh-structured basis of intercommunication.
We attempt sulfur, phosphorus, strontium, magnesium are mixed calcining Os Bovis seu Bubali porous support, by the hydroxyapatite porous of simple substance now Support is changed into the compound porous biological support of sulfur apatite containing magnesium and strontium containing good degradation characteristic.
Summary of the invention
It is an object of the invention to solve existing bone transplantation substitute material and be difficult to have concurrently that good three-dimensional intercommunication is mesh-structured, machine The problems such as tool intensity, degradability and biological activity, mix sulfur, phosphorus, magnesium, strontium simultaneously and possess natural bone ore deposit complicated exquisite three In the cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support that dimension intercommunication is mesh-structured, calcining Niu Songzhi simple substance porous hydroxyapatite is converted The degradable of doping bone active ion magnesium and strontium is containing magnesium and the sulfur apatite porous compound bio support of strontium, the degradable of the present invention It is mesh-structured with bone conductibility, degradable that sulfur apatite porous compound bio support containing magnesium and strontium has good three-dimensional intercommunication concurrently Property, preferable mechanical strength and biocompatibility；There is the whisker growth of relatively big L/D ratio simultaneously in mesh, the ratio table of material can be increased Area, may improve cell adhesion.Because local high calcium environment can be produced when being effectively mixed with osteogenic activity ion magnesium, strontium and degraded Calcium sulfate, compound bio support may possess potential osteoinductive.This compound bio support may meet bone more Transplantation substitute material or the preferable condition of bone tissue engineering stent material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of degradable contains magnesium and the sulfur apatite porous compound bio support of strontium, and its material consists of following composite parts In one: strontium sulfate/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/poly Magnesium hydrogen phosphate calcium/calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/magnesium phosphate Calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyl phosphorus Lime stone, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/sulfur Acid calcium/magnesium phosphate calcium/calcium pyrophosphate.
This compound bio timbering material of x-ray powder diffraction analysis is that the sulfur apatite porous containing active ion magnesium and strontium is combined Biologic bracket material such as strontium sulfate/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/ Polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/phosphoric acid Magnesium calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyl Apatite, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/ Calcium sulfate/magnesium phosphate calcium/calcium pyrophosphate etc..The constituent of compound bio support has preferable degradation speed more, this compound bio Timbering material may have preferably degraded.Have under simulated body fluid environment calcium, magnesium, the strontium ion of compound bio timbering material are persistently released Put.This compound bio timbering material remains the exquisite three-dimensional intercommunication mesh micro structure in cattle natural bone bone ore deposit and good machinery thereof There is the whisker growth of relatively big L/D ratio in intensity, and the interior growth of mesh simultaneously, the specific surface area of material can be increased, can improve thin Sticking of born of the same parents and albumen.Animal bone cancellous bone defect district transplant observe Bone Defect Repari cell good in support stick, breed, Differentiation, secretion bone matrix, visible pole vascularization early in support, osteogenetic process is similar to the intramembranous ossification of physiological status；See The phase of examining has no that obvious immunological rejection and inflammatory reaction, prompting compound bio timbering material have good biocompatibility, Animal bone defective region is transplanted has fast and good Bone Defect Repari also to point out compound bio timbering material possible potential osteogenic activity.
As preferably, in the described degradable sulfur apatite porous compound bio support containing magnesium and strontium, the composition in strontium accounts for and can drop Solve the 1-18% of sulfur apatite porous compound bio support gross mass containing magnesium and strontium, account for degradable containing magnesium and strontium containing magnesium component The 5-60% of sulfur apatite porous compound bio support gross mass.
As preferably, described degradable containing the sulfur apatite porous compound bio support preparation method of magnesium and strontium is: pass through Cattle is calcined Grafting Cancellous Bone Bolt ore deposit porous support process through the quaternary system containing magnesium source, strontium source, sulfur source and phosphorus source, take out and be dried After, high-temperature calcination and obtain.
As preferably, described Grafting Cancellous Bone Bolt ore deposit porous support of being calcined by cattle contains magnesium source, strontium source, sulfur source and the quaternary of phosphorus source One of selection below scheme that system processes:
Scheme one: cattle is calcined after Grafting Cancellous Bone Bolt ore deposit porous support first impregnates and be evaporated in magnesium source-strontium source composite solution, Enter back into hydro-thermal reaction in sulfur source-phosphorus source composite solution；
Scheme two: cattle is calcined after Grafting Cancellous Bone Bolt ore deposit porous support first impregnates and be evaporated in the solution of strontium source, enter back into magnesium Hydro-thermal reaction in source-sulfur source-phosphorus source composite solution.
As preferably, described hydro-thermal reaction uses incubation water heating mode, controls temperature 60-90 DEG C, 36-72 hour time.
As preferably, in scheme one, cattle calcines the solid-liquid ratio of Grafting Cancellous Bone Bolt ore deposit porous support and magnesium source-strontium source composite solution For 10g:40-80mL, cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support is 10g:40-with the solid-liquid ratio of sulfur source-phosphorus source composite solution 100mL；In scheme two, cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support is 10g:20-80mL with the solid-liquid ratio of strontium source solution, and cattle is calcined Grafting Cancellous Bone Bolt ore deposit porous support is 10g:100-200mL with the solid-liquid ratio of magnesium source-sulfur source-phosphorus source composite solution.
As preferably, the parameter of described high-temperature calcination is 750-900 DEG C and calcines 3-9 hour.
As preferably, described magnesium source is one or both in magnesium nitrate, magnesium sulfate, magnesium hydrogen phosphate；Described strontium source is nitre Acid strontium；Described sulfur source is the combination of sulphuric acid or sulphuric acid and soluble sulphate, and described soluble sulphate is magnesium sulfate and/or sulfur Acid sodium；Phosphorus source is the combination of phosphoric acid or phosphoric acid and soluble phosphate, and soluble phosphate is selected from magnesium hydrogen phosphate, phosphoric acid hydrogen Diammonium, ammonium dihydrogen phosphate, magnesium hydrogen phosphate and diammonium phosphate, magnesium hydrogen phosphate and the one in ammonium dihydrogen phosphate.
As preferably, in the described quaternary system containing magnesium source, strontium source, sulfur source and phosphorus source, magnesium ion is final concentration of 0.05-0.2mol/L, the final concentration of 0.05-0.5mol/L of strontium ion, the final concentration of 0.06-0.1mol/L of sulphuric acid, by sulphuric acid The final concentration of 0.05-0.5mol/L of sulfate radical that salt provides, the final concentration of 1.7-15.3wt% of phosphoric acid, phosphate the phosphorus provided Final concentration of 0.05-0.5mol/L.Sulfate comprises the sulfate in magnesium source, sulfur source.Phosphate comprises the phosphorus in magnesium source, sulfur source Hydrochlorate.
As preferably, described degradable sulfur apatite porous its material of compound bio support containing magnesium and strontium can gradient fall Solve；The described degradable sulfur apatite porous compound bio support containing magnesium and strontium maintains cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support Three-dimensional intercommunication is mesh-structured and mechanical strength, have the whisker growth of relatively big L/D ratio, whisker draw ratio in mesh is 5-simultaneously 20:1, can be effectively increased the specific surface area of material, and described degradable contains magnesium and the sulfur apatite porous compound bio bracket holes of strontium Gap rate 70-85%, aperture 400-1400 μm.
As preferably, the preparation method of described cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support is:
(1) bone bar or bone piece that bovine cancellous bone cuts into thick 0.5-2cm obtain material bone；
(2) material bone is placed in the interior steaming and decocting 40-60min in pressure cooker of distilled water, then cleans dry with 40-60 DEG C of drinking water Only, this step 4-6 time is repeated；
(3) by step (2) process after material bone in constant temperature oven 80-120 DEG C dry 12-24 hour, be subsequently placed in In calcining furnace, calcine 8-12 hour for 900-1200 DEG C, after cooling, obtain cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support.
The invention has the beneficial effects as follows:
The present invention can stablize effectively by strontium, magnesium, sulfur, phosphorus incorporation calcining bovine cancellous bone ore deposit porous support, by simple substance hydroxyl Apatite porous support converts the abundant degradable of change of component containing magnesium and the sulfur apatite porous compound support frame material such as sulfur of strontium Acid strontium/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/ Calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/magnesium phosphate calcium/hydroxy-apatite Stone, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/ Calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/calcium sulfate/magnesium phosphate Calcium/calcium pyrophosphate etc..The present invention is effectively mixed with osteogenic activity ion magnesium ion, strontium ion and sulfate ion, phosphonium ion etc.； Being strontium sulfate containing strontium composition, strontium sulfate quality accounts for the 1.0-18% of material gross mass；Containing magnesium component for having good degradation characteristic Tricresyl phosphate magnesium calcium or polyphosphoric acids hydrogen magnesium calcium etc., account for the 5-60% of material gross mass containing magnesium component；Part compound rest is containing tool There are very fast degradation speed, energy complete biodegradable and have the calcium sulfate of potential bone-inducting active ion；Part compound rest also contains There are hydroxyapatite and/or calcium pyrophosphate.
Compound bio timbering material maintains natural bone bone ore deposit three-dimensional intercommunication mesh micro structure and preferable mechanical strength thereof, Having the pencil whisker growth compared with big L/D ratio in mesh, whisker draw ratio is 5-20:1 simultaneously, can be effectively increased the ratio table of material Area and improve cell adhesion.Owing to the component of compound bio support possesses preferable degradation characteristic more, therefore compound bio props up Frame material may possess preferable molten drop characteristic.Material still can keep good mechanical strength and mesh after the molten fall of larger proportion Structure, these can be confirmed in simulated body fluid molten fall experiment, visible containing magnesium, the molten fall of strontium sulfur apatite compound rest under Electronic Speculum With redeposited.When the porous compound bio timbering material of the present invention is transplanted in animal Grafting Cancellous Bone Bolt defective region, it is seen that repair thin What born of the same parents were good raise, stick, proliferation and differentiation, secretion substrate and quickly vasoganglion formed, material can realize similar physiological status Intramembranous ossification, the prompting good bone conductibility of compound bio support and potential bone-inducting active；Do not find during observation Immunological rejection and significantly inflammation, prompting compound bio support possesses good biocompatibility.
In a word, the compound bio timbering material of the present invention have concurrently good three-dimensional intercommunication mesh-structured with bone conductibility, can drop Xie Xing, preferable mechanical strength and biocompatibility；There is the whisker growth of relatively big L/D ratio simultaneously in mesh, the ratio of material can be increased Surface area improves cell adhesion.Because being effectively mixed with osteogenic activity ion magnesium and strontium, portion of material is the most effectively mixed with can be complete Biological fall is degraded and can produce the calcium sulfate of local high calcium environment, and compound bio timbering material may possess potential self-bone grafting Property.This compound bio support may meet the preferable bar of bone transplantation substitute material or bone tissue engineering stent material more Part.
Accompanying drawing explanation
Fig. 1 is a kind of scanning electron microscope (SEM) photograph of product of the present invention.
Fig. 2 is that product of the present invention is in simulated body fluid molten fall experiment calcium value (n=3, human serum calcium ion reference value 2-in early days 2.67mmol/l)。
The scanning electron microscope (SEM) photograph of material after a kind of simulated body fluid molten fall experiment of Fig. 3 product of the present invention.
Fig. 4 is a kind of transplantation experiments histology's diagram in early days of product of the present invention.
Fig. 5 is another kind of transplantation experiments histology's diagram in early days of product of the present invention.
Fig. 6 is a kind of transplantation experiments later stage phase histology diagram of product of the present invention.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in further detail.
In the present invention, if not refering in particular to, the raw material used and equipment etc. are all commercially available or commonly used in the art. Method in following embodiment, if no special instructions, is the conventional method of this area.
The preparation example 1 of cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support:
(1) the bone bar that bovine cancellous bone (cattle condyle of femur spongy bone) cuts into thick 0.5cm obtains material bone；
(2) material bone is placed in interior steaming and decocting 40 minutes in pressure cooker of distilled water, then cleans up with 40 DEG C of water, repeats this Step 6 time；
(3) material bone after step (2) being processed is 80 DEG C dry 24 hours in constant temperature oven, are subsequently placed in calcining furnace In, 900 DEG C (heating rate 10 DEG C/min) is calcined 12 hours, obtains cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support after furnace cooling.Cattle The preparation example 2 of calcining Grafting Cancellous Bone Bolt ore deposit porous support:
(1) bone piece that bovine cancellous bone (cattle condyle of femur spongy bone) cuts into thick 1 obtains material bone；
(2) material bone is placed in the interior steaming and decocting 60min in pressure cooker of distilled water, then cleans up with 60 DEG C of water, repeats this Step 4 time；
(3) material bone after step (2) being processed is 120 DEG C dry 12 hours in constant temperature oven, are subsequently placed in calcining furnace In, 1200 DEG C (heating rate 10 DEG C/min) is calcined 8 hours, obtains cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support after furnace cooling.
The preparation example 3 of cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support:
(1) the bone bar that bovine cancellous bone (cattle condyle of femur spongy bone) cuts into thick 0.8 obtains material bone；
(2) material bone is placed in the interior steaming and decocting 50min in pressure cooker of distilled water, then cleans up with 50 DEG C of water, repeats this Step 5 time；
(3) material bone after step (2) being processed is 100 DEG C dry 18 hours in constant temperature oven, are subsequently placed in calcining furnace In, 1000 DEG C (heating rate 10 DEG C/min) is calcined 10 hours, obtains cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support after furnace cooling.
Total embodiment 1:
A: by the final concentration of 0.05-of magnesium ion in the described quaternary system containing magnesium source, strontium source, sulfur source and phosphorus source 0.2mol/L, the final concentration of 0.05-0.5mol/L of strontium ion；The final concentration of 0.06-0.1mol/L of sulphuric acid, is provided by sulfate The final concentration of 0.05-0.5mol/L of sulfate radical, the final concentration of 1.7-15.3wt% of phosphoric acid, phosphate the phosphorus final concentration provided Dispensing is carried out for 0.05-0.5mol/L.
B: weigh strontium nitrate, magnesium nitrate and first prepare strontium nitrate, magnesium nitrate solution, cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support with Magnesium source-strontium source composite solution solid-to-liquid ratio is 10g:40-80 milliliter；Cattle is calcined Grafting Cancellous Bone Bolt ore deposit porous support, and to immerse strontium, magnesium multiple Closing in solution, after impregnating 15-30 minute, microwave is evaporated: microwave output power 300-500w, 15-24 minute time.
C: calcining Grafting Cancellous Bone Bolt ore deposit porous support with sulfur source, the solid-to-liquid ratio of phosphorus source composite solution by cattle is 10g:40-100 milli Rising preparation sulfur source, phosphorus source composite solution, the cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support after step B being processed immerses dipping and hydro-thermal Reacting, hydro-thermal reaction takes incubation water heating to react, and controls reaction temperature 60 DEG C, and the response time is 12 hours.
D: in taking-up porous support constant temperature oven, 70-90 DEG C is dried product 24-48 hour.
E: the cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support after step D being processed is in being placed in calcining furnace, and 900 DEG C (heat up speed Rate 2.5 DEG C/min) calcine 3-9 hour, obtain cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support converting material after furnace cooling.
Total embodiment 2:
A: by the final concentration of 0.05-of magnesium ion in the described quaternary system containing magnesium source, strontium source, sulfur source and phosphorus source 0.2mol/L, the final concentration of 0.05-0.5mol/L of strontium ion；The final concentration of 0.06-0.1mol/L of sulphuric acid, is provided by sulfate The final concentration of 0.05-0.5mol/L of sulfate radical, the final concentration of 1.7-15.3wt% of phosphoric acid, phosphate the phosphorus final concentration provided Dispensing is carried out for 0.05-0.5mol/L.
B: weigh strontium nitrate and first prepare strontium nitrate solution, cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support and strontium source solution solid-to-liquid ratio For 10g:20-80 milliliter；Cattle is calcined Grafting Cancellous Bone Bolt ore deposit porous support and immerses in the solution of strontium source, microwave after impregnating 15-30 minute It is evaporated: microwave output power 300-500w, 15-30 minute time.
C: by the solid-liquid ratio of magnesium source-sulfur source-phosphorus source composite solution be 10g:100-200mL preparation magnesium source-sulfur source-phosphorus source multiple Closing solution, the cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support processed by magnesium source-sulfur source-phosphorus source composite solution immersion step B soaks Stain and hydro-thermal reaction, hydro-thermal reaction takes incubation water heating to react, and controls reaction temperature 70-90 DEG C, and the response time is that 20-36 is little Time.
D: in taking-up cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support to constant temperature oven, 70-90 DEG C is dried product 24-48 hour.
E: the cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support after step D being processed is in being placed in calcining furnace, and 750-900 DEG C (rises Temperature speed 2.5 DEG C/min) calcine 2-9 hour, obtain product after furnace cooling.
Each sample carries out gross examination of skeletal muscle and carries out X-ray powder diffraction (Xray diffraction, XRD) analysis；Select Sample segment carries out carrying out displaing microstructure observing with scanning electron microscope；It is simulated body fluid molten fall experiment, the animal of bone defect healing Experiment etc..Gross examination of skeletal muscle observes the general form of material, intensity etc., sample segment INSTRON 5566 test compression intensity. Simulated body fluid molten fall experiment as simulated body fluid, detects the solid-liquid mass body of material and simulated body fluid with medical sodium chloride injection Long-pending ratio, for 1-2 gram: 100 milliliters, has been inserted in lid beaker, is simulated body fluid molten fall experiment, molten fall under 37 DEG C of constant temperatures During experiment 30 days, calcium, phosphorus, magnesium, strontium ion in 3 days label taking this use AU5800 automatic clinical chemistry analyzers detect simulated body fluid Measuring, simulated body fluid 40% was changed at every 3 days in first 15 days of molten fall, and the later stage is changed without simulated body fluid；Survey with domestic electronic balance Determine the quality of sample after molten fall is tested 30 days and calculate degradation rate；Carry out molten fall experiment start before, at the end of the XRD analysis of material With scanning electron microscopic observation etc..8 healthy new zealand white rabbits of animal bone defect repair test and Selection, cause diameter at rabbit femoral condyle The Cranial defect of 8mm, uses porous composite biological material to carry out bone defect healing, within postoperative 1,2,4,12 weeks, puts to death laboratory animal, enter The histological examination of row bone defect healing.
Embodiment 1
605242
Take magnesium nitrate 0.51 gram, strontium nitrate 0.42 in beaker, prepare 0.1mol/L magnesium nitrate, 0.1mol/L strontium nitrate 20 Milliliter, calcines Grafting Cancellous Bone Bolt ore deposit porous support 5 grams with the cattle of porosity about 70-85% and adsorbs half an hour, and in microwave, low fire is dried 6 × 2 minutes；Take 2 milliliters of sulphuric acid, phosphoric acid 3.5 milliliters preparation 0.1mol/L sulphuric acid, 15.3w% phosphoric acid solution 20 milliliters, cattle is forged Burn Grafting Cancellous Bone Bolt ore deposit porous support put into wherein 60 DEG C react 12 hours, take out latter 90 DEG C and be dried 24 hours；Intensification 2.5 per minute DEG C to 900 DEG C, it is down to room temperature with stove after maintaining 3 hours and obtains 605242A；Intensification per minute 2.5 DEG C to 900 DEG C, after maintaining 6 hours It is down to room temperature with stove and obtains 605242E；Intensification per minute 2.5 DEG C to 900 DEG C, is down to room temperature with stove after maintaining 9 hours and obtains 605242K；
Embodiment 2
605243
Take magnesium nitrate 0.51 gram, strontium nitrate 0.84 in beaker, prepare 0.1mol/L magnesium nitrate, 0.2mol/L strontium nitrate 20 Milliliter, calcines Grafting Cancellous Bone Bolt ore deposit porous support 5 grams with the cattle of porosity about 70-85% and adsorbs half an hour, and in microwave, low fire is dried 6 × 2 minutes；Take 2 milliliters of sulphuric acid, phosphoric acid 3.5 milliliters preparation 0.1mol/L sulphuric acid, 15w% phosphoric acid solution 20 milliliters, cattle is calcined Grafting Cancellous Bone Bolt ore deposit porous support puts into wherein, 60 DEG C of dippings, hydro-thermal reaction 12 hours, take out rear 90 DEG C dry 24 hours；Every point Clock heats up 2.5 DEG C to 900 DEG C, is down to room temperature with stove and obtains 605243A after maintaining 2 hours；Take out latter 90 DEG C and be dried 24 hours weight 9- 10.5 grams；Intensification per minute 2.5 DEG C to 900 DEG C, is down to room temperature with stove after maintaining 3 hours and obtains 605243A；Intensification 2.5 per minute DEG C to 900 DEG C, it is down to room temperature with stove after maintaining 6 hours and obtains 605243E；Intensification per minute 2.5 DEG C to 900 DEG C, after maintaining 9 hours It is down to room temperature with stove obtain
Embodiment 3
605244
Take magnesium nitrate 1.53 grams, strontium nitrate 3.17 grams in beaker, prepare 0.2mol/L magnesium nitrate, 0.5mol/L strontium nitrate 30 milliliters, calcining Grafting Cancellous Bone Bolt ore deposit porous support 5 grams with the cattle of porosity about 70-85% and adsorb half an hour, in microwave, low fire is done Dry 6 × 2 minutes；Take 3 milliliters of 1mol/L sulphuric acid, anhydrous sodium sulfate 2.16 grams, 85w% phosphoric acid 0.6 milliliter, diammonium phosphate 1.58 Gram preparation 0.3mol/L sodium sulfate, 0.1mol/L sulphuric acid, 1.7w% phosphoric acid, 0.4mol/L ammonium dibasic phosphate solution 30 milliliters, use Its submergence cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support, 60 DEG C of dippings, hydro-thermal reaction 12 hours, take out rear 90 DEG C dry 24 hours； Intensification per minute 2.5 DEG C to 900 DEG C, is down to room temperature with stove after maintaining 3 hours and obtains 605244A；Intensification per minute 2.5 DEG C is to 900 DEG C, it is down to room temperature with stove after maintaining 6 hours and obtains 605244E；Intensification per minute 2.5 DEG C to 900 DEG C, drops with stove after maintaining 9 hours 605244K is obtained to room temperature.
Embodiment 4
605245
Take magnesium nitrate 0.77 gram, strontium nitrate 2.54 in beaker, prepare 0.1mol/L magnesium nitrate, 0.4mol/L strontium nitrate 30 Milliliter, calcines Grafting Cancellous Bone Bolt ore deposit porous support 5 grams with the cattle of porosity about 85% and adsorbs half an hour, and in microwave, low fire is dried 6 × 2 Minute；Take 3 milliliters of 1mol/L sulphuric acid, anhydrous sodium sulfate 1.44 grams, diammonium phosphate 0.79 gram preparation 0.1mol/L sulphuric acid, 0.2mol/L sodium sulfate, 0.2mol/L ammonium dibasic phosphate solution 20 milliliters, calcines Grafting Cancellous Bone Bolt ore deposit porous support with its submergence cattle, 60 DEG C of dippings, hydro-thermal reactions are reacted 12 hours, take out latter 90 DEG C and are dried 24 hours；Intensification per minute 2.5 DEG C to 900 DEG C, maintains 3 It is down to room temperature with stove after hour and obtains 605245A；Intensification per minute 2.5 DEG C to 900 DEG C, is down to room temperature with stove after maintaining 9 hours and obtains 605245K；
Embodiment 6
605246
Take magnesium nitrate 0.77 gram, strontium nitrate 1.27 grams in beaker, prepare 0.1mol/L magnesium nitrate, 0.2mol/L strontium nitrate 30 milliliters, calcining Grafting Cancellous Bone Bolt ore deposit porous support 5 grams with the cattle of porosity about 85% and adsorb half an hour, in microwave, low fire is dried 6 × 2 minutes；Take 3 milliliters of 1 mol/L sulphuric acid, anhydrous sodium sulfate 0.72 gram, diammonium phosphate 0.4 gram preparation 0.1 mol/L sulfur Acid, 0.1 mol/L ammonium dibasic phosphate solution 30 milliliters, calcine cattle Grafting Cancellous Bone Bolt ore deposit porous support and put into wherein, 60 DEG C of reactions 12 hours, take out latter 90 DEG C and be dried 24 hours weights gram；Intensification per minute 2.5 DEG C to 900 DEG C, is down to room with stove after maintaining 2 hours Warm 605246A；Intensification per minute 2.5 DEG C to 900 DEG C, is down to room temperature with stove after maintaining 3 hours and obtains 605246A；Liter per minute Temperature 2.5 DEG C to 900 DEG C, is down to room temperature with stove after maintaining 6 hours and obtains 605246E；Intensification per minute 2.5 DEG C to 900 DEG C, maintains 9 It is down to room temperature with stove after hour and obtains 605246K；
Embodiment 7
509032
By preparation 0.05mol/L strontium nitrate, 0.08mol/L sulphuric acid, 0.3mol/L sodium sulfate, 0.2mol/L magnesium hydrogen phosphate, 1.7w% phosphoric acid composite solution 100 milliliters calculate dispensing: strontium nitrate 1.06 grams, 5 milliliters of 1mol/L sulphuric acid, 4.26 grams of sodium sulfate, Magnesium hydrogen phosphate 3.46 grams, 85w% phosphoric acid 2 milliliters；First take strontium nitrate 1.06 grams and add deionized water preparation containing strontium solution 40 milliliters, use The cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support 10 grams of porosity 70-85% impregnates half an hour, microwave output power 500-700 watt Within 24-30 minute, it is evaporated；Take 10 milliliters of 1mol/L sulphuric acid, 4.26 grams of sodium sulfate, magnesium hydrogen phosphate 3.46 grams, 85w% phosphoric acid 2 milliliters add Deionized water preparation sulfur, phosphorus, magnesium composite solution 100 milliliters, immerse wherein with its submergence cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support, Beaker is counter covers protection lower 70 DEG C of constant temperature dipping, hydro-thermal reaction taking-up in 20 hours, and 80 DEG C are dried 24 hours；Intensification per minute 2.5 DEG C To 750 DEG C, it is down to room temperature with stove after maintaining 6 hours and obtains 509032E；
Embodiment 8
601291
By preparation 0.1mol/L strontium nitrate, 0.05mol/L magnesium sulfate, 0.1mol/L sulphuric acid, 0.15mol/L sodium sulfate, 0.1mol/L magnesium hydrogen phosphate, 1.7w% phosphoric acid compound system 100 milliliters calculate dispensing；First take strontium nitrate, Magnesium sulfate heptahydrate preparation Magnesium source-strontium source composite solution 20 milliliters；Grafting Cancellous Bone Bolt ore deposit porous support 5 grams dipping half is calcined little with the cattle of porosity about 85% Time, 500 watts of microwave is evaporated for 8 × 2 minutes；Take 10 milliliters of 1mol/L sulphuric acid, 2.26 grams of sodium sulfate, magnesium hydrogen phosphate 1.74 grams, 85w% Phosphoric acid 2 milliliters preparation 0.05mol/L sulphuric acid, 0.15mol/L sodium sulfate, 0.1mol/L magnesium hydrogen phosphate, 1.7w% phosphoric acid are combined molten Liquid 100 milliliters；Cattle being calcined Grafting Cancellous Bone Bolt ore deposit porous support put into wherein, beaker is counter covers dipping, water under lower 90 DEG C of constant temperatures Heat treatment takes out for 24 hours, and 90 DEG C are dried 24 hours；Intensification per minute 2.5 DEG C to 900 DEG C, is down to room with stove after maintaining 8 hours Warm 603292E；
603292E
SrSO46.2%
CaSO445.3%
Ca2.89Mg0.11(PO4)248.5%.
Embodiment 9
601294
Preparation 0.3mol/L strontium nitrate, 0.05mol/L magnesium sulfate, 0.1mol/L sulphuric acid, 0.1mol/L magnesium hydrogen phosphate, 1.7w% phosphoric acid composite solution 100 milliliters calculates dispensing: strontium nitrate 3.18 grams, Magnesium sulfate heptahydrate 0.65 gram, 1mol/L sulphuric acid 5 are in the least Liter, 2.13 grams of sodium sulfate, magnesium hydrogen phosphate 0.86 gram, 85w% phosphatase 11 milliliter；First take strontium nitrate 3.18 grams, Magnesium sulfate heptahydrate 0.65 Gram add deionized water preparation strontium nitrate, magnesium sulfate composite solution 20 milliliters；The cattle of porosity about 85% is calcined Grafting Cancellous Bone Bolt ore deposit Porous support 5 grams puts into and wherein impregnates half an hour, and 500 watts of microwave is evaporated for 8 × 2 minutes；Take 5 milliliters of 1mol/L sulphuric acid, 85w% phosphorus Acid 1 milliliter, magnesium hydrogen phosphate 0.86 gram add deionized water preparation composite solution 50 milliliters, many with its submergence cattle calcining Grafting Cancellous Bone Bolt ore deposit Hole support, dipping, hydrothermal treatment consists 24 hours under 70 DEG C of constant temperatures, take out latter 80 DEG C and be dried 48 hours；Intensification per minute 2.5 DEG C To 900 DEG C, it is down to room temperature with stove after maintaining 6 hours and obtains 603294E；
603294E
SrSO410.3%
CaSO459.8%
Ca2.89 Mg0.11(PO4)229.9%.
Embodiment 10
509052
By preparation 0.05mol/L strontium nitrate, 0.1mol/L sulphuric acid, 0.3mol/L sodium sulfate, 0.05mol/L magnesium hydrogen phosphate, 1.7w% phosphoric acid, 100 milliliters of compound systems calculating dispensings of 0.5mol/L ammonium dihydrogen phosphate composite solution: strontium nitrate 1.06,1mol/ 10 milliliters of L sulphuric acid, 4.26 grams of sodium sulfate, magnesium hydrogen phosphate 0.86 gram, ammonium dihydrogen phosphate 5.78 grams, phosphoric acid 2 milliliters；First take strontium nitrate 1.06 preparation strontium nitrate solutions 20 milliliters, calcine Grafting Cancellous Bone Bolt ore deposit porous support 10 grams by the cattle of porosity about 85% and put into wherein Impregnating half an hour, 500 watts of microwave is evaporated for 6 × 2 minutes；Take 10 milliliters of 1mol/L sulphuric acid, 4.26 grams of sodium sulfate, magnesium hydrogen phosphate 0.86 Gram, ammonium dihydrogen phosphate 5.78 grams, phosphoric acid 2 milliliters add deionized water preparation sulfur, phosphorus, magnesium composite solution 100 milliliters, with its submergence cattle Calcining Grafting Cancellous Bone Bolt ore deposit porous support, beaker is counter covers lower 70 DEG C of constant temperature dipping, hydro-thermal reaction was taken out after 20 hours, ph value about 2.5； 80 DEG C are dried 48 hours；Intensification per minute 2.5 DEG C to 750 DEG C, is down to room temperature with stove after maintaining 6 hours and obtains 509052E；
Embodiment 11
512121
By preparation 0.05mol/L strontium nitrate, 0.1mol/L magnesium sulfate, 0.1mol/L sulphuric acid, 0.4mol/L sodium sulfate, 1.7w% phosphoric acid, 0.4mol/L diammonium phosphate composite solution 50 milliliters calculate dispensing: strontium nitrate 0.5 gram, 1.3 grams of magnesium sulfate, 5 milliliters of sulphuric acid, 2.84 grams of sodium sulfate, 85w% phosphatase 11 milliliter, diammonium phosphate 2.64 grams；First take 1.3 grams of strontium nitrate, magnesium sulfate Add deionized water preparation strontium nitrate, Adlerika 20 milliliters, calcine Grafting Cancellous Bone Bolt ore deposit porous with the cattle of porosity 70-85% and prop up 5 grams of frame impregnates half an hour, and microwave output power 300-500 watt is evaporated for 30 minutes；Take 5 milliliters of 1mol/L sulphuric acid, sodium sulfate 2.84 Gram, 85w% phosphatase 11 milliliter, diammonium phosphate 2.64 grams preparation composite solution 50 milliliters, with its submergence cattle calcining Grafting Cancellous Bone Bolt ore deposit Porous support, beaker is counter covers lower 90 DEG C of constant temperature dipping, hydro-thermal reaction taking-up in 36 hours, takes out latter 70 DEG C and is dried 48 hours；Every point Clock heats up 2.5 DEG C to 750 DEG C, is down to room temperature with stove and obtains 512121E after maintaining 6 hours；Intensification per minute 2.5 DEG C to 750 DEG C, dimension It is down to room temperature with stove after holding 9 hours and obtains 512121K；
Testing result:
Material gross examination of skeletal muscle, strength detection, XRD component analysis and scanning electron microscopic observation
The prefabricated form of various products intact holding bovine cancellous bone, without fragmentation, avalanche or powdered etc., has preferable machine Tool intensity；The 1-4 specimen INSTRON 5566 spongy bone test compression intensity of 10 × 10 × 10mm is shown in Table 1.X-ray diffraction (XRD) detection confirms dipping and the calcining cattle pine bone ore deposit support of hydro-thermal reaction in strontium, magnesium, sulfur, phosphorus solution, through calcining after being dried The degradable sulfur apatite porous compound bio timbering material such as strontium sulfate/magnesium phosphate calcium/pyrophosphoric acid mixing magnesium, strontium can be converted into Calcium, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate/hydroxyapatite, Strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium Calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/ Hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/calcium sulfate/magnesium phosphate calcium/calcium pyrophosphate etc., becomes containing strontium Strontium sulfate is divided to account for the 1-18% of material gross mass；It is magnesium phosphate calcium or magnesium hydrogen phosphate calcium containing magnesium component, accounts for material containing magnesium component total The 5-60% of quality；Compound rest containing have very fast degradation speed, can be degradable and have the sulfur of potential bone-inducting active ion Acid calcium；Part compound rest is possibly together with hydroxyapatite.Electron-microscope scanning finds (with reference to Fig. 1), and product maintains bovine cancellous bone certainly So agent structure of the three-dimensional intercommunication mesh micro structure in bone bone ore deposit, the calcium sulfate crystal whiskers simultaneously having relatively big L/D ratio in mesh is raw Long, whisker draw ratio is the specific surface area that 5-20:1 can increase material, may improve cell adhesion.
Table 1 compressive strength
2, the external molten fall experiment of material
Simulated body fluid molten fall experiment as simulated body fluid, detects the solid-liquid of material and simulated body fluid with medical chloride injection Mass volume ratio is 1-2 gram: 100 milliliters, has inserted in lid beaker, is simulated the molten fall of body fluid real under 37 DEG C of constant temperatures Test, molten fall experimental period 4 weeks, measure with calcium, phosphorus, magnesium plasma in AU5800 automatic clinical chemistry analyzer detection simulated body fluid, The quality of material calculate degradation rate when measuring 4 weeks with domestic electronic balance；Carry out molten fall experiment start before, at the end of material XRD analysis and scanning electron microscopic observation etc..Experiment finds that material has preferable degradation rate (table 2), the early stage (half of simulated body fluid experiment In month) most sample simulated body fluids there is higher calcium ion concentration i.e. to maintain human serum normal reference value (2-2.67mmol/ L) between 1-4 times of intermediate value (Fig. 2)；The most active ion magnesium, strontium discharge.At the end of molten fall experiment, stent mesh becomes big, machine Tool intensity is good (table 3).The XRD analysis of simulated body fluid experiment material finds, the composition of material and mass ratio change over and Change, calcium sulfate and containing magnesium, zinc phosphorus apatite composition etc. gradually decrease or disappear, timbering material fades to hydroxy-apatite Stone.Scanning electron microscope can find the molten fall of material and redeposited (Fig. 3) of mineralogical composition.
Table 2 material soaks the degradation rate (n=3) of 4 weeks in simulated body fluid
Compressive strength after table 3 molten fall experiment
3, animal bone defect repair test
The transplanting of porous composite biological material group (1 week) i.e. visible cell in early days, blood vessel enter the whole space of support, can See repairing cell proliferation, break up, secrete bone matrix (Fig. 4)；2, within 4 weeks, i.e. having bone trabecula to be formed, freshman bone tissue has had with support Beautiful combination (Fig. 5)；Lamellar bone within 12 weeks, is had to form (Fig. 6).Bone Defect Repari does not finds immunological rejection during observing soon and well And obvious inflammation, material possesses good biocompatibility.
Embodiment described above is the one preferably scheme of the present invention, not makees the present invention any pro forma Limit, on the premise of without departing from the technical scheme described in claim, also have other variant and remodeling.

Claims (10)

1. a degradable is containing magnesium and the sulfur apatite porous compound bio support of strontium, it is characterised in that: its material consist of as One in lower composite parts: strontium sulfate/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, sulfur Acid strontium/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, sulphuric acid Strontium/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate Calcium/hydroxyapatite, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, Strontium sulfate/calcium sulfate/magnesium phosphate calcium/calcium pyrophosphate.
A kind of degradable the most according to claim 1 contains magnesium and the sulfur apatite porous compound bio support of strontium, its feature It is: in the described degradable sulfur apatite porous compound bio support containing magnesium and strontium, the composition in strontium accounts for degradable and contains magnesium and strontium The 1-18% of sulfur apatite porous compound bio support gross mass, accounts for degradable containing magnesium and the sulfur apatite porous of strontium containing magnesium component The 5-60% of compound bio support gross mass.
A kind of degradable the most according to claim 1 and 2 contains magnesium and the sulfur apatite porous compound bio support of strontium, and it is special Levy and be: described degradable containing the sulfur apatite porous compound bio support preparation method of magnesium and strontium is: by by cattle calcining pine Matter bone bone ore deposit porous support processes through the quaternary system containing magnesium source, strontium source, sulfur source and phosphorus source, takes out dried, high-temperature calcination And obtain.
A kind of degradable the most according to claim 3 contains magnesium and the sulfur apatite porous compound bio support of strontium, its feature It is: the described choosing that cattle is calcined the quaternary system process that Grafting Cancellous Bone Bolt ore deposit porous support contains magnesium source, strontium source, sulfur source and phosphorus source Select one of below scheme:
Scheme one: cattle is calcined after Grafting Cancellous Bone Bolt ore deposit porous support first impregnates and be evaporated in magnesium source-strontium source composite solution, then enter Enter hydro-thermal reaction in sulfur source-phosphorus source composite solution；
Scheme two: cattle is calcined after Grafting Cancellous Bone Bolt ore deposit porous support first impregnates and be evaporated in the solution of strontium source, enter back into magnesium source-sulfur Hydro-thermal reaction in source-phosphorus source composite solution.
A kind of degradable the most according to claim 4 contains magnesium and the sulfur apatite porous compound bio support of strontium, its feature It is: described hydro-thermal reaction uses incubation water heating mode, controls temperature 60-90 DEG C, 36-72 hour time.
A kind of degradable the most according to claim 4 contains magnesium and the sulfur apatite porous compound bio support of strontium, its feature Being: in scheme one, cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support is 10g:40-with the solid-liquid ratio of magnesium source-strontium source composite solution 80mL, cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support is 10g:40-100mL with the solid-liquid ratio of sulfur source-phosphorus source composite solution；Scheme two In, cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support is 10g:20-80mL with the solid-liquid ratio of strontium source solution, and cattle calcining Grafting Cancellous Bone Bolt ore deposit is many Hole support is 10g:100-200mL with the solid-liquid ratio of magnesium source-sulfur source-phosphorus source composite solution.
A kind of degradable the most according to claim 3 contains magnesium and the sulfur apatite porous compound bio support of strontium, its feature It is: the parameter of described high-temperature calcination is 750-900 DEG C and calcines 3-9 hour.
A kind of degradable the most according to claim 3 contains magnesium and the sulfur apatite porous compound bio support of strontium, its feature Being, described magnesium source is one or both in magnesium nitrate, magnesium sulfate, magnesium hydrogen phosphate；Described strontium source is strontium nitrate；Described sulfur source For the combination of sulphuric acid or sulphuric acid with soluble sulphate, described soluble sulphate is magnesium sulfate and/or sodium sulfate；Phosphorus source For the combination of phosphoric acid or phosphoric acid with soluble phosphate, soluble phosphate is selected from magnesium hydrogen phosphate, diammonium phosphate, biphosphate Ammonium, magnesium hydrogen phosphate and diammonium phosphate, magnesium hydrogen phosphate and the one in ammonium dihydrogen phosphate.
A kind of degradable the most according to claim 8 contains magnesium and the sulfur apatite porous compound bio support of strontium, its feature It is: the final concentration of 0.05-0.2mol/L of magnesium ion, strontium in the described quaternary system containing magnesium source, strontium source, sulfur source and phosphorus source The final concentration of 0.05-0.5mol/L of ion, the final concentration of 0.06-0.1mol/L of sulphuric acid, sulfate the sulfate radical provided is eventually Concentration is 0.05-0.5mol/L, the final concentration of 1.7-15.3wt% of phosphoric acid, phosphate the final concentration of 0.05-of phosphorus provided 0.5mol/L。
A kind of degradable the most according to claim 1 and 2 contains magnesium and the sulfur apatite porous compound bio support of strontium, its It is characterised by: described degradable can gradient degradation containing sulfur apatite porous its material of compound bio support of magnesium and strontium；Described can The degraded sulfur apatite porous compound bio support containing magnesium and strontium maintains the three-dimensional mutual of cattle calcining Grafting Cancellous Bone Bolt ore deposit porous support Logical mesh-structured and mechanical strength, have the whisker growth of relatively big L/D ratio, whisker draw ratio in mesh is 5-20:1 simultaneously, can have Effect increases the specific surface area of material, and described degradable contains magnesium and sulfur apatite porous compound bio brace aperture rate 70-of strontium 85%, aperture 400-1400 μm.
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